CN114987011A - Copper-clad plate, printed circuit board comprising same and application thereof - Google Patents

Copper-clad plate, printed circuit board comprising same and application thereof Download PDF

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Publication number
CN114987011A
CN114987011A CN202210811070.XA CN202210811070A CN114987011A CN 114987011 A CN114987011 A CN 114987011A CN 202210811070 A CN202210811070 A CN 202210811070A CN 114987011 A CN114987011 A CN 114987011A
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CN
China
Prior art keywords
copper
resin
clad plate
parts
glass fiber
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CN202210811070.XA
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Chinese (zh)
Inventor
霍翠
熊博明
殷卫峰
刘锐
李莎
张记明
曾耀德
师剑英
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Shengyi Technology Shaanxi Co ltd
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Shengyi Technology Shaanxi Co ltd
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Priority to CN202210811070.XA priority Critical patent/CN114987011A/en
Publication of CN114987011A publication Critical patent/CN114987011A/en
Pending legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/036—Multilayers with layers of different types
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08J2361/04, C08J2361/18, and C08J2361/20
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2371/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
    • C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention provides a copper-clad plate, a printed circuit board comprising the same and application thereof, wherein the copper-clad plate comprises at least one prepreg and copper foils arranged on one side or two sides of the prepreg; the prepreg comprises glass fiber paper and a thermosetting resin composition attached to the glass fiber paper; the passive intermodulation value of the copper-clad plate is less than or equal to-153 dBc under the frequency of 700-2600 MHz. The copper-clad plate forms a uniform and stable system through compounding of the glass fiber paper and the thermosetting resin composition, so that the PIM effect of the copper-clad plate in a full frequency band is remarkably improved, the preparation process of the copper-clad plate is simple, the cost is low, the problem of the glass fiber effect in the prior art is solved, the transmission rate of signals and data of a printed circuit board, an antenna and the like containing the copper-clad plate is higher, the quality is higher, the PIM coordination is better, and the integrity of transmitted information can be ensured in the transmission of 5G and future higher frequencies.

Description

Copper-clad plate, printed circuit board comprising same and application thereof
Technical Field
The invention belongs to the technical field of copper-clad plate materials, and particularly relates to a copper-clad plate, a printed circuit board comprising the copper-clad plate and application of the printed circuit board.
Background
With the continuous development of electronic communication technology, especially the coming of 5G technology in recent years, in order to quickly transmit large-capacity data and high-definition voice and video signals, it is required to be implemented in a higher frequency band, so that new requirements are put on various performances of Printed Circuit Boards (PCBs), and especially passive intermodulation of signals and PIM signal transmission of PCB plates, which have not been paid much attention before, are beginning to be paid much attention.
Passive Inter-Modulation (PIM), also called intermodulation distortion, is caused by the non-linear characteristics of various Passive devices in the radio frequency system. In high power, multi-channel systems, the non-linear characteristics of these passive devices may generate frequency components relative to the operating frequency, and these frequency components and the operating frequency mix together and enter the operating system, and if these unwanted frequency components are large enough, they may affect the normal operation of the communication system. When the spurious intermodulation signal falls within the receiving frequency band of the base station, the sensitivity of the receiver is reduced, thereby causing the reduction of the call quality or the carrier-to-interference ratio of the system, and the reduction of the capacity of the communication system, the PIM becomes an important parameter for limiting the system capacity, and the PIM is mainly generated among various capacitance and inductance passive devices in a radio frequency system, respectively sends out frequencies of different frequency bands, and mutually influences signal transmission.
The antenna must be designed and manufactured to have minimum passive intermodulation PIM specifications to achieve its best performance in crowded signal environments. The PCB board is an important part of the antenna, and the PCB is processed by a copper-clad plate, so that the performance of the copper-clad plate for the antenna also plays a key factor for the PIM index of the antenna, the level of the performance determines the actual PIM performance to a great extent, particularly when the environmental factors (such as temperature and humidity change) are considered, a specific copper-clad plate with low PIM performance is crucial to realizing a certain PIM level of a wireless communication system, and the quality of the signal and data transmission process can be ensured only when the PIM value is smaller.
In the existing copper-clad plate production process, epoxy resin with good bonding performance and low cost is widely used, but the epoxy resin copper-clad plate has high dielectric constant and dielectric loss and insufficient high-frequency characteristic, cannot adapt to the development trend of high frequency and cannot meet the signal transmission requirement of an antenna. In order to satisfy the high frequency requirement, using a crosslinkable polyolefin resin is a feasible method, for example, CN102304264A discloses a high frequency copper foil substrate and a composite material used thereof, which comprises 10 to 50 wt% of a reinforcing material and 50 to 90 wt% of a resin mixture comprising a high molecular weight polybutadiene resin, a low molecular weight polybutadiene resin, a modified polyphenylene ether thermosetting resin, an inorganic powder, a flame retardant, a crosslinking agent, an adhesion promoter and a hardening initiator; the high-frequency copper foil substrate containing the composite material has the use frequency of more than 1GHz, has low dielectric constant and loss factor, and still has insufficient PIM performance.
For example, CN107197598A discloses a low PIM high performance microwave high frequency composite ceramic substrate and a method for preparing the same, wherein polytetrafluoroethylene powder and low temperature co-fired ceramic powder are mixed, and are ball-milled by a ball mill to prepare a microwave high frequency ceramic insulating medium material layer, a low temperature ceramic sheet is dipped in polytetrafluoroethylene dispersion liquid and sintered at high temperature to prepare a low PIM ceramic bonding sheet, and a matte copper foil layer, the low PIM ceramic bonding sheet and the insulating medium material layer are bonded and press-molded to obtain the ceramic substrate with low PIM value. However, the substrate obtained by the sintering method has a problem of insufficient uniformity in thickness, dielectric constant, and the like, and it is difficult to realize a low PIM value over the entire band.
Therefore, it is important to develop a circuit material having a low PIM value in the full band and good overall performance in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a copper-clad plate, a printed circuit board comprising the copper-clad plate and application of the copper-clad plate.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a copper-clad plate, which comprises at least one prepreg and copper foils arranged on one side or two sides of the prepreg; the prepreg comprises glass fiber paper and a thermosetting resin composition attached to the glass fiber paper; the passive intermodulation value (PIM value) of the copper-clad plate under the frequency of 700-2600MHz is less than or equal to-153 dBc.
The copper-clad plate provided by the invention takes the glass fiber paper as a reinforcing material, the filling property is excellent, the porous loose property can be filled with more thermosetting resin compositions, so that the copper-clad plate realizes more functionalization, and in addition, the glass fiber paper reinforcing material avoids the Skaew effect of the traditional glass cloth. According to the invention, through compounding of the glass fiber paper and the thermosetting resin composition, a uniform and stable system is formed, the PIM effect of the copper-clad plate in the full frequency band is obviously improved, the preparation process of the copper-clad plate is simple, the cost is low, and the problems of glass fiber effect (glass fiber cloth is woven in warp and weft directions, gaps exist in the middle, resin can fill the glass fiber cloth, and the transmission speed of signals in glass fiber and resin is different, namely the glass fiber effect) in the prior art are solved, so that a printed circuit board, an antenna and the like containing the copper-clad plate have better signal transmission quality and higher signal transmission speed, the PIM coordination is better, the integrity of signals can be ensured in the transmission process of 5G and future higher frequency signals, and especially the advantages of big data, high definition audio frequency, video transmission and the like are more obvious.
In the invention, the passive intermodulation value (PIM value) is measured by adopting a method known in the art, and with reference to IEC-63037, the PIM value test of the intermodulation performance of the electronic circuit substrate in the frequency range of 700-2600MHz or even wider can be realized, and an intermodulation reference value is provided for the intermodulation design of the whole terminal.
In the present invention, the 700-2600MHz is a full frequency band covering low frequency to high frequency, including 800MHz, 900MHz, 1000MHz, 1100MHz, 1200MHz, 1300MHz, 1400MHz, 1500MHz, 1600MHz, 1700MHz, 1800MHz, 1900MHz, 2000MHz, 2100MHz, 2200MHz, 2300MHz, 2400MHz, or 2500MHz, and specific values between the above values are limited to sections and for simplicity, and the present invention does not exhaust the specific values included in the range.
The copper-clad plate has a PIM value of less than or equal to-153 dBc in a full frequency band of 700-2600MHz, and the industry roughly classifies intermodulation: when the PIM value reaches-143 dBc, the PIM value is the better intermodulation; when the PIM value reaches-153 dBc, the PIM value is very good intermodulation; when the PIM value reaches-163 dBc, it is excellent intermodulation. The PIM value of the copper-clad plate is less than or equal to-153 dBc, the copper-clad plate has good intermodulation level, the PIM value can be-154 dBc, -155dBc, -156dBc, -158dBc, -160dBc, -161dBc, -165dBc, -167dBc, -169dBc or-170 dBc, and the like, and even the PIM value can be less than or equal to the excellent intermodulation level of-163 dBc.
Preferably, the passive intermodulation value of the copper-clad plate under the frequency of 700-2600MHz is less than or equal to-158 dBc.
Preferably, the glass fiber paper has a basis weight (mass per unit area) of 20-105g/m 2 For example, it may be 25g/m 2 、30g/m 2 、40g/m 2 、50g/m 2 、60g/m 2 、70g/m 2 、80g/m 2 、90g/m 2 Or 100g/m 2 And the specific values between the foregoing, are not intended to be exhaustive or to limit the invention to the precise values encompassed within the scope, for reasons of brevity and clarity.
Preferably, the glass fiber in the glass fiber paper comprises any one of E-glass fiber, NE-glass fiber or S-glass fiber.
Preferably, the adhesive in the fiberglass paper is an aqueous resin adhesive.
Preferably, the adhesive in the glass fiber paper comprises any one of an aqueous epoxy adhesive, an aqueous acrylic adhesive or an aqueous polytetrafluoroethylene adhesive.
As a preferable technical scheme of the invention, the basis weight of the glass fiber paper is 20-105g/m 2 The glass fiber is E-glass fiber, NE-glass fiber or S-glass fiber, and the three kinds of glass fibers are electronic-grade glass fibers, so that the glass fiber is suitable for the field of electronic products and has good insulating property, and plays a decisive role in the electrical properties of the CCL and the PCB to a certain extent; the adhesive preferably comprises a water-based epoxy adhesive, a water-based acrylic adhesive or a water-based polytetrafluoroethylene adhesive, and the water-based epoxy adhesive has excellent heat resistance and stability, and the water-based acrylic adhesive and the water-based polytetrafluoroethylene adhesive have the heat resistance and stability in consideration of the heat resistance and the dielectric property of the plate on the other handThe copper clad laminate has low polarity, better dielectric property for the laminate as a whole, and easy realization of the property for low-dielectric and ultra-low-loss laminates in particular, and can be used as a reinforcing material to be compounded with a thermosetting resin composition, so that the copper clad laminate has good intermodulation, low PIM value and excellent comprehensive performance. If the basis weight of the fiberglass paper is too low or too high, or the fiberglass and/or the adhesive are not the preferred type of the invention, the intermodulation performance of the copper-clad plate can be influenced to a certain extent, so that the PIM value is increased.
Preferably, the thermosetting resin composition comprises a combination of a resin material and a filler.
Preferably, the thermosetting resin composition comprises, in parts by mass: 60-160 parts of resin material and 50-450 parts of filler.
Wherein the resin material is 60-160 parts, such as 70 parts, 80 parts, 90 parts, 100 parts, 110 parts, 120 parts, 130 parts, 140 parts or 150 parts, and the specific values therebetween are not exhaustive for the purpose of brevity and clarity.
The filler is 50 to 450 parts, such as 60 parts, 80 parts, 100 parts, 120 parts, 150 parts, 180 parts, 200 parts, 220 parts, 250 parts, 280 parts, 300 parts, 320 parts, 350 parts, 380 parts, 400 parts, 420 parts or 440 parts, and specific points therebetween, which are not intended to be space-wise and for the sake of brevity, the invention is not intended to be exhaustive of the specific points included in the ranges set forth.
Preferably, the resin material is a high-frequency resin material, and comprises any one of cyanate ester resin, polyphenylene oxide resin, polybutadiene resin, styrene-butadiene resin, bismaleimide resin, polytetrafluoroethylene resin, polyimide resin, epoxy resin, liquid crystal resin, benzoxazine resin, phenoxy resin or nitrile rubber or a combination of at least two of the cyanate ester resin, the polyphenylene oxide resin, the polybutadiene resin, the styrene-butadiene resin, the bismaleimide resin, the polytetrafluoroethylene resin, the polyimide resin, the epoxy resin, the liquid crystal resin, the benzoxazine resin, the phenoxy resin or the nitrile rubber.
Preferably, the resin material comprises any one of cyanate ester resin, polyphenylene oxide resin, polybutadiene resin, benzoxazine resin, epoxy resin or bismaleimide resin or the combination of at least two of the cyanate ester resin, the polyphenylene oxide resin, the polybutadiene resin, the benzoxazine resin, the epoxy resin or the bismaleimide resin; exemplary combinations include, but are not limited to: a combination of a polyphenylene ether resin and a bismaleimide resin, a combination of a polyphenylene ether resin and a polybutadiene resin, a combination of a polyphenylene ether resin, a bismaleimide resin and a polybutadiene resin, a combination of a benzoxazine resin and a cyanate ester resin, and a combination of an epoxy resin and a cyanate ester resin.
Preferably, the epoxy resin includes any one of dicyclopentadiene (DCPD) -type epoxy resin, bisphenol a epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, novolac epoxy resin, biphenyl-type epoxy resin, phenol novolac epoxy resin, bisphenol a novolac epoxy resin, silicone-modified epoxy resin, phosphorous-containing epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin, or o-cresol epoxy resin, or a combination of at least any two thereof.
Preferably, the filler comprises a spherical filler.
As a preferred technical scheme of the invention, the spherical filler is compounded with a thermosetting resin material, so that the thermosetting resin composition has the properties of high frequency and low dielectric loss; the thermosetting resin composition containing the spherical filler is attached to the glass fiber paper and fully filled in the porous structure of the glass fiber paper, so that a uniform, stable and compact structure is formed, a prepreg and a copper-clad plate have high-frequency characteristics, the dielectric property is good, the PIM value is low, the intermodulation performance requirement of a full frequency band can be met, and the signal transmission rate is faster and the quality is higher.
Preferably, the filler comprises any one or a combination of at least two of silica, titania, alumina, barium titanate, strontium titanate, magnesium titanate, calcium titanate, barium strontium titanate, barium calcium titanate, lead zirconate titanate, lead lanthanum zirconate titanate, barium lanthanum titanate, barium zirconium titanate, hafnium dioxide, lead magnesium niobate, barium magnesium niobate, lithium niobate, potassium niobate, strontium aluminum tantalate, potassium tantalum niobate, barium strontium niobate, barium lead niobate, barium titanium niobate, strontium bismuth tantalate, bismuth titanate, barium rubidium titanate, copper titanate, or lead titanate-lead magnesium niobate.
In a preferred embodiment, the thermosetting resin composition comprises, in parts by mass: 40-80 parts (for example, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, etc.) of polyphenylene ether resin, 5-15 parts (for example, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, etc.) of bismaleimide resin, 30-65 parts (for example, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, etc.) of polybutadiene resin, and 50-450 parts of filler.
In another preferred embodiment, the thermosetting resin composition comprises, in parts by mass: 50-100 parts of benzoxazine resin (such as 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts or 95 parts), 20-60 parts of cyanate ester resin (such as 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts or 55 parts) and 50-450 parts of filler.
In another preferred embodiment, the thermosetting resin composition comprises, in parts by mass: 70-110 parts (such as 75 parts, 80 parts, 85 parts, 90 parts, 95 parts, 100 parts or 105 parts) of cyanate ester resin, 10-50 parts (such as 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts or 45 parts) of epoxy resin and 50-450 parts of filler.
Preferably, the thermosetting resin composition further comprises any one or a combination of at least two of an accelerator, a flame retardant, an initiator, a curing agent or a crosslinking agent.
Preferably, the accelerator comprises any one or a combination of at least two of imidazole compounds, organometallic complexes, tertiary amines, tertiary phosphines or quaternary ammonium salts.
Preferably, the imidazole compound includes any one of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2-phenyl-4-methylimidazole, 2-dodecylimidazole or 1-cyanoethyl-2-methylimidazole or a combination of at least two thereof.
Preferably, the thermosetting resin composition includes 0.01 to 5 parts by mass of an accelerator, for example, the accelerator may be 0.05 parts, 0.1 parts, 0.2 parts, 0.5 parts, 0.8 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, or the like.
Preferably, the initiator comprises any one of organic peroxide, organic amine, organic phosphine, phosphate, phosphite ester, phosphoric acid, phenolic compound, imidazole compound, boron trifluoride and complex compound thereof or the combination of at least two of the organic peroxide, the organic amine, the organic phosphine, the phosphate ester, the phosphite ester, the phosphoric acid, the phenolic compound, the imidazole compound, the boron trifluoride and the complex compound thereof, and the organic peroxide is further preferred.
Preferably, the initiator includes any one of α, α' -bis (t-butylperoxy-m-isopropyl) benzene, dicumyl peroxide, t-butylperoxyisopropyl benzene, 1-bis (t-hexylperoxy) -3,3, 5-trimethylcyclohexane, 2, 5-dimethyl-2, 5-bis (t-butylperoxy) -3-hexyne, t-butylperoctoate, t-butylperoxybenzoate, triethylammonium or a salt thereof, a quaternary ammonium salt compound, 2,4, 6-tris (dimethylaminomethylamine) phenol, benzyldimethylamine, imidazoles, tripentylphenolate amine, monophenol compounds, polyphenol compounds, boron trifluoride and an organic complex thereof, triphenyl phosphate or triphenyl phosphite, or a combination of at least two thereof.
Preferably, the thermosetting resin composition includes 0.01 to 5 parts by mass of the initiator, for example, the initiator may be 0.05 parts, 0.1 parts, 0.2 parts, 0.5 parts, 0.8 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, or the like.
Preferably, the crosslinking agent comprises one or a combination of at least two of triallyl isocyanurate, triallyl polyisocyanurate, triallyl cyanurate, trimethacrylic acid, diallyl phthalate, divinylbenzene, or multifunctional acrylates.
Preferably, the thermosetting resin composition includes 0.01 to 10 parts by mass of a crosslinking agent, for example, the crosslinking agent may be 0.05 parts, 0.1 parts, 0.2 parts, 0.5 parts, 0.8 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, or the like.
Preferably, the flame retardant comprises any one of a halogen-based flame retardant, a phosphorus-based flame retardant or a nitrogen-based flame retardant or a combination of at least two of them, and further preferably a bromine-containing flame retardant and/or a phosphorus-based flame retardant.
Preferably, the thermosetting resin composition is attached to the glassfiber paper after being impregnated and dried.
Preferably, the preparation method of the prepreg comprises the following steps: and infiltrating glass fiber paper with the resin glue solution of the thermosetting resin composition, and then drying to obtain the prepreg.
Preferably, the resin glue solution comprises a thermosetting resin composition and a solvent, and the thermosetting resin composition is dissolved or dispersed in the solvent.
The addition amount of the solvent is selected by the technical personnel according to the process requirements, so that the resin glue solution can reach the viscosity suitable for use, and the resin composition can be conveniently impregnated and coated. And in the subsequent drying, semi-curing or complete curing link, the solvent can be partially or completely volatilized.
The solvent is not particularly limited, and generally, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene and mesitylene, esters such as ethyl acetate, butyl acetate and ethoxyethyl acetate, alcohols such as methanol, ethanol and butanol, ethers such as ethyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether, diethylene glycol ethyl ether (carbitol) and diethylene glycol monobutyl ether (butyl carbitol), nitrogen-containing compounds such as N, N-dimethylformamide, N-dimethylacetamide and N-methyl-2-pyrrolidone; the solvents may be used alone or in combination of two or more. Preferably any one or the combination of at least two of methanol, ethanol, acetone, butanone, toluene, ethylene glycol monobutyl ether, methyl acetate, ethyl acetate or cyclohexanone.
Illustratively, the preparation method of the resin glue solution comprises the following steps: and (3) mixing the resin material with a solvent, an optional accelerator, a flame retardant, an initiator, a curing agent and a crosslinking agent, adding a filler, and uniformly dispersing to obtain the resin glue solution.
Preferably, the drying temperature is 50-180 deg.C, such as 60 deg.C, 70 deg.C, 80 deg.C, 85 deg.C, 90 deg.C, 95 deg.C, 100 deg.C, 105 deg.C, 110 deg.C, 115 deg.C, 120 deg.C, 125 deg.C, 130 deg.C, 135 deg.C,
140 ℃, 145 ℃, 150 ℃, 155 ℃, 160 ℃, 165 ℃ or 170 ℃ and the like.
Preferably, the drying time is 0.5-30min, for example, 1min, 2min, 3min, 5min, 8min, 10min, 15min, 20min or 25 min.
Preferably, the number of prepregs in the copper-clad plate is 1-20, for example, 2,5, 8, 10, 12, 15 or 18 prepregs can be used.
Preferably, the preparation method of the copper-clad plate comprises the following steps: pressing copper foil on one side or two sides of one prepreg, and curing to obtain the copper-clad plate; or laminating at least two prepregs into a laminated board, then pressing copper foils on one side or two sides of the laminated board, and curing to obtain the copper-clad plate.
Preferably, the curing is performed in a press.
Preferably, the curing temperature is 120-.
Preferably, the curing pressure is 1-10MPa, such as 1.5MPa, 2MPa, 3MPa, 4MPa, 5MPa, 6MPa, 7MPa, 8MPa or 9MPa, and the like.
Preferably, the curing time is 30-150min, such as 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min, 120min, 130min, 140min, 145min, or the like.
In a second aspect, the invention provides a printed circuit board comprising the copper-clad plate according to the first aspect.
In a third aspect, the invention provides an application of the copper-clad plate according to the first aspect or the printed circuit board according to the second aspect in an antenna.
Compared with the prior art, the invention has the following beneficial effects:
the copper-clad plate provided by the invention takes the glass fiber paper as a reinforcing material, and the glass fiber paper and the thermosetting resin composition are compounded, so that the copper-clad plate has a passive intermodulation value of less than or equal to-157 dBc under 700 plus 2600MHz, and can reach a very good intermodulation level of less than or equal to-163 dBc, the PIM effect of the copper-clad plate in the full frequency band is obviously improved, the preparation process of the copper-clad plate is simple, the cost is low, the problem of glass fiber effect in the prior art is solved, the dielectric loss Df of the plate under 10GHz is less than or equal to 0.003, even less than or equal to 0.0023, the whole copper-clad plate has excellent dielectric property and low dielectric loss, and therefore, the signals and data transmission rate of a printed circuit board, an antenna and the like comprising the copper-clad plate are faster, the quality is higher, the PIM coordination is better, and the integrity of transmission information can be ensured in the transmission of 5G and the higher frequency in the future.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Materials used in the following embodiments of the invention include:
(1) reinforcing material
Glass fiber paper: the specific specification information for the glassfiber paper of examples 1-9 is shown in Table 1:
TABLE 1
Glass fiber paper Weight per unit (g/m) 2 ) Adhesive (Water-based) Glass fiber Manufacturer of the product
W1 20 Aqueous epoxy E-glass fiber All-grass of Japanese
W2 50 Aqueous epoxy E-glass fiber Huate's capsule
W3 75 Aqueous epoxy E-glass fiber Huate's capsule
W4 75 Aqueous acrylic acid NE-glass fiber Huate's capsule
W5 75 Aqueous epoxy NE-glass fiber Huate's capsule
W6 75 Aqueous Polytetrafluoroethylene (PTFE) NE-glass fiber Huate's capsule
W7 75 Aqueous PTFE E-glass fiber Huate's capsule
W8 75 Aqueous PTFE S-glass fiber 'Huate' a chemical synthesis
W9 10 Aqueous epoxy E-glass fiber Prince of Japan
W10 120 Aqueous epoxy E-glass fiber Huate's capsule
Glass fiber cloth: 1078 of glass fiber cloth with a single weight of 47g/m 2 The glass fiber is NE-glass fiber.
(2) Resin material
Polyphenylene ether resin, SA9000, sapick corporation;
polybutadiene resin, B-3000, Nippon Caoda;
bismaleimide resin, D939, available from east sichuan province;
benzoxazine resin, LZ-32, available from oasis;
cyanate ester resin, XU71787, available from dow chemistry;
epoxy resins, dicyclopentadiene (DCPD) type epoxy resins, D206, available from east sichuan.
(3) Spherical filler
Silicon dioxide, particle diameter D 50 5 μm, purchased from juniper, jiang;
titanium dioxide, particle diameter D 50 8 μm, purchased from Shandong China;
alumina, particle diameter D 50 5 μm, available from brocade, Suzhou.
(4) Accelerator (b): 2-methylimidazole (2-MI), BASF (Germany);
(5) initiator: dicumyl peroxide, science and technology of Hubei Jusheng;
(6) a crosslinking agent: triallyl isocyanurate, science and technology of Hubei Jusheng.
Example 1
A copper-clad plate comprises 2 prepregs and copper foils arranged on two sides of the prepregs; the prepreg comprises glass fiber paper W1 (the information is detailed in Table 1) and a thermosetting resin composition attached to the glass fiber paper W1; the thermosetting resin composition comprises the following components in parts by mass: 60 parts of polyphenylene ether resin, 10 parts of bismaleimide resin, 50 parts of polybutadiene resin, 1.2 parts of dicumyl peroxide and 290 parts of silicon dioxide.
The preparation method of the copper-clad plate comprises the following steps:
(1) mixing the thermosetting resin composition with a solvent (butanone/toluene in a mass ratio of 1.1:1) according to the formula amount, and uniformly mixing at room temperature to prepare a resin glue solution with a solid content of 65%; impregnating the resin glue solution with glass fiber paper W1, and drying in an oven at 150 ℃ for 5min to obtain a single weight of 480g/m 2 The prepreg of (a);
(2) after laminating 2 prepregs, placing the prepregs between two copper foils (1OZ, from Lusenberg), laminating for 60min at 220 ℃ and 4MPa in a press, and curing to obtain the copper-clad plate.
Examples 2 to 11, comparative example 1
A copper-clad plate which is different from the copper-clad plate in example 1 in the types of reinforcing materials and/or the components of the thermosetting resin composition, and is specifically shown in tables 2 and 3; the mass units of the components in tables 2 to 3 are all parts, and the preparation method of each copper-clad plate is the same as that of example 1.
TABLE 2
Figure BDA0003739073450000131
TABLE 3
Figure BDA0003739073450000141
The copper clad was tested for the following properties:
(1) PIM value: referring to the IEC-63037, the method realizes the intermodulation performance test of the electronic circuit substrate, realizes the data test by adopting a PIM/passive intermodulation tester in a microwave darkroom, and tests the PIM values under the frequencies of 700MHz, 800MHz, 1900MHz and 2600MHz respectively:
(2) high-frequency dielectric properties: referring to IEC-61189, testing the dielectric constant Dk and dielectric loss Df of the plate at 10GHz by using an SPDR method commonly used in the field;
the test results are shown in table 4:
TABLE 4
Figure BDA0003739073450000151
According to the data in table 4, the copper-clad plate provided by the invention takes the glass fiber paper as a reinforcing material, and the compounding of the glass fiber paper and the thermosetting resin composition not only obviously improves the PIM effect of the copper-clad plate in the full frequency band and enables the PIM value to reach an extremely low level from-157 dBc to-166 dBc, but also has the advantages of simple preparation process and low cost, and solves the problem of glass fiber effect in the prior art, thereby having better signal transmission quality, faster signal transmission rate and better PIM harmony. By combining the embodiments 1 to 11, the further optimization of the PIM harmony of the copper-clad plate can be realized by adjusting and selecting the basis weight of the glass fiber paper, the glass fiber and the adhesive.
The reinforcing material in comparative example 1 was 1078 glass cloth, and compared with examples 1 to 11, the PIM of the copper clad laminate was inferior, and the improvement could not be achieved even though NE-glass fiber was used, probably because the glass cloth had nodes in the warp and weft directions, which produced the skiw effect, and the compounding effect with the thermosetting resin composition was not good, which resulted in signal transmission loss and poor PIM.
In addition, the dielectric property test results in table 4 show that the dielectric constant and the dielectric loss of the samples of examples 1 to 11 are tested by the SPDR method at a high frequency of 10GHz, the dielectric loss is less than or equal to 0.003, even less than or equal to 0.0023, the dielectric property and the low dielectric loss are integrally shown, and the use requirements of the antenna copper-clad plate are met.
The applicant declares that the invention is described by the above embodiments of the copper-clad plate, the printed circuit board comprising the copper-clad plate and the application thereof, but the invention is not limited to the above embodiments, that is, the invention is not meant to be implemented only by relying on the above embodiments. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. The copper-clad plate is characterized by comprising at least one prepreg and copper foils arranged on one side or two sides of the prepreg; the prepreg comprises glass fiber paper and a thermosetting resin composition attached to the glass fiber paper; the passive intermodulation value of the copper-clad plate is less than or equal to-153 dBc under the frequency of 700-2600 MHz.
2. The copper-clad plate of claim 1, wherein the passive intermodulation value of the copper-clad plate is less than or equal to-158 dBc under the frequency of 700-2600 MHz.
3. The copper-clad plate according to claim 1 or 2, wherein the basis weight of the fiberglass paper is 20-105g/m 2 ；
Preferably, the glass fiber in the glass fiber paper comprises any one of E-glass fiber, NE-glass fiber or S-glass fiber;
preferably, the adhesive in the fiberglass paper comprises any one of an aqueous epoxy adhesive, an aqueous acrylic adhesive or an aqueous polytetrafluoroethylene adhesive.
4. The copper-clad plate according to any one of claims 1 to 3, wherein the thermosetting resin composition comprises a combination of a resin material and a filler;
preferably, the thermosetting resin composition comprises, in parts by mass: 60-160 parts of resin material and 50-450 parts of filler.
5. The copper-clad plate according to claim 4, wherein the resin material comprises any one or a combination of at least two of cyanate ester resin, polyphenylene ether resin, polybutadiene resin, styrene-butadiene resin, bismaleimide resin, polytetrafluoroethylene resin, polyimide resin, epoxy resin, liquid crystal resin, benzoxazine resin, phenoxy resin or nitrile rubber;
preferably, the resin material includes any one of cyanate ester resin, polyphenylene ether resin, polybutadiene resin, benzoxazine resin, epoxy resin or bismaleimide resin or a combination of at least two thereof.
6. The copper-clad plate according to claim 4 or 5, wherein the filler comprises a spherical filler;
preferably, the filler comprises any one or a combination of at least two of silica, titania, alumina, barium titanate, strontium titanate, magnesium titanate, calcium titanate, barium strontium titanate, barium calcium titanate, lead zirconate titanate, lead lanthanum zirconate titanate, barium lanthanum titanate, barium zirconium titanate, hafnium oxide, lead magnesium niobate, barium magnesium niobate, lithium niobate, potassium niobate, strontium aluminum tantalate, potassium tantalum niobate, barium strontium niobate, lead barium niobate, barium titanium niobate, strontium bismuth tantalate, bismuth titanate, barium rubidium titanate, copper titanate, or lead titanate-lead magnesium niobate.
7. The copper-clad plate according to any one of claims 4 to 6, wherein the thermosetting resin composition further comprises any one or a combination of at least two of an accelerator, a flame retardant, an initiator, a curing agent or a crosslinking agent;
preferably, the accelerator comprises any one of imidazole compounds, organometallic complexes, tertiary amines, tertiary phosphines or quaternary ammonium salts or a combination of at least two of the same;
preferably, the initiator comprises an organic peroxide;
preferably, the crosslinking agent comprises one or a combination of at least two of triallyl isocyanurate, triallyl polyisocyanurate, triallyl cyanurate, trimethacrylic acid, diallyl phthalate, divinylbenzene, or multifunctional acrylates.
8. The copper-clad plate according to any one of claims 1 to 7, wherein the thermosetting resin composition is attached to the fiberglass paper by dipping, drying;
preferably, the number of prepregs in the copper-clad plate is 1-20.
9. A printed circuit board comprising the copper-clad laminate of any one of claims 1-8.
10. Use of the copper-clad plate according to any one of claims 1 to 8 or the printed circuit board according to claim 9 in an antenna.
CN202210811070.XA 2022-07-11 2022-07-11 Copper-clad plate, printed circuit board comprising same and application thereof Pending CN114987011A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101220160A (en) * 2007-12-07 2008-07-16 广东生益科技股份有限公司 Prepreg applied for multi-layer board of printed electronic circuit
CN201797648U (en) * 2010-09-21 2011-04-13 广东生益科技股份有限公司 PCB board favorable for improving impedance control of PCB
CN108130784A (en) * 2017-12-26 2018-06-08 陕西华特新材料股份有限公司 E all-glass papers for CEM-3 copper coated foil plates and preparation method thereof
CN111867239A (en) * 2019-04-24 2020-10-30 广东生益科技股份有限公司 Copper-clad laminate and printed circuit board
US20210298169A1 (en) * 2020-03-20 2021-09-23 Iteq Corporation Resin composition, prepreg, and printed circuit board

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101220160A (en) * 2007-12-07 2008-07-16 广东生益科技股份有限公司 Prepreg applied for multi-layer board of printed electronic circuit
CN201797648U (en) * 2010-09-21 2011-04-13 广东生益科技股份有限公司 PCB board favorable for improving impedance control of PCB
CN108130784A (en) * 2017-12-26 2018-06-08 陕西华特新材料股份有限公司 E all-glass papers for CEM-3 copper coated foil plates and preparation method thereof
CN111867239A (en) * 2019-04-24 2020-10-30 广东生益科技股份有限公司 Copper-clad laminate and printed circuit board
US20210298169A1 (en) * 2020-03-20 2021-09-23 Iteq Corporation Resin composition, prepreg, and printed circuit board

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